Method of forming photographic images

ABSTRACT

D R A W I N G wherein R represents a hydrogen atom or a methyl group, and M1 and M2 each represents a member selected from the group consisting of a hydrogen atom, a lithium atom, a sodium atom, a potassium atom and an ammonium group, whereby the occurrence of reticulation decreases and anti-adhesive properties are improved.     and repeating units represented by the formula (II)   A method of forming photographic images which comprises developing at above 30*C a photographic sensitive material comprising a support having thereon at least one photosensitive emulsion layer and a surface layer comprising a hydrophilic binder and containing a copolymer containing repeating units represented by the formula (I)

United States Patent [191 Nagatomo et al.

[ 1 Apr. 15, 1975 METHOD OF FORMING PHOTOGRAPHIC IMAGES [73] Assignee:Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22] Filed: Apr. 23, 1974 [21] App]. No.: 463,321

[30] Foreign Application Priority Data Apr. 27, 1973 Japan 48-47735 [52]US. Cl 96/50 R; 96/67; 96/87 R [51] Int. Cl G03c 5/26 [58] Field ofSearch 96/50 PL, 114.1, 67, 87, 96/87 A, 50

[56] References Cited UNITED STATES PATENTS 3,468,664 9/1969 Stewart96/95 3,503,743 3/1970 Kosar 96/67 3,591,379 7/1971 Plakunov 96/503,597,208 8/1971 Nishio et a1 96/67 3,816,136 6/1974 Goffe et al 96/66FOREIGN PATENTS OR APPLICATIONS 482,204 3/1938 United Kingdom 96/50 PL933,391 8/1963 United Kingdom 96/50 PL OTHER PUBLICATIONS McGraw, C. W.,et al., Def. Publ. of Serial No.t89,324 filed 11-13-70, Published in 8270.0.6 on June 1, 1971, Def. Publ. No. T887,012, 96-67.

Primary Examiner-Ronald H. Smith Attorney, Agent, or Firm-Sughrue,Rothwell, Mion, Zinn and Macpeak [57] ABSTRACT A method of formingphotographic images which comprises developing at above 30C aphotographic sensitive material comprising a support having thereon atleast one photosensitive emulsion layer and a surface layer comprising ahydrophilic binder and containing a copolymer containing repeating unitsrepresented by the formula (I) -CH2CH- and repeating units representedby the formula (II) CH CH l I (II) C0011, C0011;

wherein R represents a hydrogen atom or a methyl group, and M and M eachrepresents a member selected from the group consisting of a hydrogenatom, a lithium atom, a sodium atom, a potassium atom and an ammoniumgroup, whereby the occurrence of reticulation decreasesand anti-adhesiveproperties are improved.

10 Claims, N0 Drawings METHOD OF FORMING PHOTOGRAPHIC IMAGES BACKGROUNDOF THE INVENTION 1. Field of the Invention The present invention relatesto photographic sensitive materials and particularly to a method offorming photographic images wherein the occurrence of reticulation isvery small, high speed processing can be carried out at a hightemperaure and anti-adhesive properties are improved.

2. Description of the Prior Art Exposed photographic sensitive materialsare generally processed at 30C or less. If the temperature of theprocessing is increased, it becomes possible to shorten the period oftime for processing, because the speed of processing, such asdevelopment and fixing of the silver halide or the color developmentthereof, increases with an increase in the temperature. However, if sucha rapid processing is carried out, reticulation of the photosensitivematerials in the processing solutions at a high temperature and thequality of images obtained after development remarkably deteriorates.

For example, if.the material is processed at 495C, conventional emulsionlayers are excessively swelled and sometimes the emulsion layerdelaminates from the support due to the occurrence of reticulation onthe treated film. As a method of solving this problem, the addition of alarge amount of a hardening agent to the photosensitive materials hasbeen suggested. However, this method adversely affects the photographicemulsions or delays the speed of processing. Hence, it is necessary toprevent occurrence of reticulation in the processing of photographicsensitive materials and particularly multi-layer color photographicsensitive materials at a high temperature using other methods differentfrom the above described method in which a large amount of a hardeningagent is added.

Further, photographic sensitive materials have a surface layercontaining a hydrophilic high molecular weight compound such as gelatinas a binder. Therefore, the surface of the photographic sensitivematerial is easily influenced by the temperature and easily becomessticky.

For example, when photographic sensitive materials are stored at highhumidity and particularly in an atmosphere of a high humidity and a hightemperature, they easily stick to each other or to other materials oncontact because the adhesivity and stickiness thereof remarkablyincrease. Such adhesion phenomenon is very disadvantageous because theadhesion is brought about between the photographic materials themselvesor between the photographic sensitive material and other materialscontacted therewith during production, exposure, processing, projectionor storage of the photographic sensitive materials.

SUMMARY OF THE INVENTION An object of the present invention is toprovide a method of forming photographic images wherein the occurrenceof reticulation at high temperature processing is inhibited and theanti-adhesive properties are improved.

As the result of much research, the present inventors have found thatthe occurrence of reticulation in development of photographic sensitivematerials at high layer containing a specific high molecular weightcompound. Furthermore, it has been found that the occurrence ofreticulation can be inhibited in providing such a surface layer, even ifhigh speed drying is carried out at production of the photographicsensitive materials.

The invention provides a method of forming photographic images whichcomprises developing at a temperature of above 30C a photographicsensitive material comprising a support having thereon at least onephotosensitive emulsion layer and a surface layer comprising ahydrophilic binder and containing a copolymer including repeating unitsrepresented by the formula (I) CH2 CH and repeating units represented bythe formula (II) CH CH COOM; COOM wherein R represents a hydrogen atomor a methyl group, M and M each represents a member selected from thegroup consisting of a hydrogen atom. a lithium atom, a sodium atom, apotassium atom and an ammonium group, whereby occurrence of reticulationdecreases and the anti-adhesive properties are improved.

DETAILED DESCRIPTION OF THE INVENTION In the following, the presentinvention will be described in greater detail.

The high molecular weight compounds used in the present invention arethose produced by copolymcrizing styrene or methyl styrene and maleicacid or maleic acid anhydride and hydrolyzing the resulting copolymer,which have repeating units represented by the following general formulae(1) and (II) CH CH COOP l COOM;

wherein R represents a hydrogen atom or a methyl group and M and M eachrepresents H, Li, Na, K or NH4.

Of course, copolymers having these units can contain, if desired, one ormore other polymerizable monomers so long as the hydrophilic propertiesthereof are not injured. Such polymerizable monomer components includethe alkyl esters of acrylic acid and methacrylic acid (e.g., methylmethacrylate, ethyl acrylate, hydroxyethyl acrylate, propyl acrylate,cyclohexyl acrylate, Z-ethylhexyl acrylate, decyl acrylate, B-cyanoethylacrylate, B-chloroethyl acrylate, 2-ethoxyethyl acrylate, sulfopropylmethacrylate and the like), vinyl ethers (e.g., methylvinyl ether, butylvinyl ether, oleyl vinyl ether and the like), vinyl ketones (e.g.,methyl vinyl ketone, ethyl vinyl ketone and the like), styrenederivatives (e.g., dimethyl styrene, 2,4,6-trimethylstyrene,ethylstyrene, laurylstyrene, chlorostyrene, dichlorostyrene,methoxystyrene, cyanostyrene, dimethylaminostyrene, chloromethylstyrene,vinylbenzoic acid, styrene sulfonic acid, a-methylstyrene and the like),vinyl heterocyclic compounds (e.g., vinylpyridine, vinylpyrrolidone,vinylisoxazolidone, vinylimidazole and the like), acrylonitrile, vinylchloride, vinylidene chloride, ethylene propylene, butadiene, isoprene,chloroprene, itaconic acid anhydride, citraconic acid anhydride andvinyl sulfonic acid.

In the polymerization reaction, acetone, methanol, isopropanol, methylethyl ketone, tetrahydrofuran, dimethylformamide, benzene or a mixturethereof can be used as a solvent. The quantity of the monomers chargedcan be suitably varied, for example, the monomers can be used in a rangeof about 20 to 150 percent by weight to the solvent.

As polymerization initiators, conventional radical polymeriza tioncatalysts such as azobisisobutyronitrile, 2,2'-azobis-(2,4-valeronitrile1,1 -azobis- (cyclohexanel -carbonitrile), 2,2-azobis(4-methyl-2,4-dimethyl valeronitrile) and benzoyl peroxide can be effectively used.The amount of the catalysts is about 0.1 to 5 percent by weight, andpreferably is 0.5 to 2.0 percent by weight based on the weight of themonomers from an operational viewpoint. Further, the polymerizationreaction is carried out by heating at about 60 to 80C in an inertatmosphere, e.g., a nitrogen atmosphere, for about 3 to 6 hours. Theproduced polymers are used after neutralizing or hydrolyzing with anaqueous alkali solution, such as lithium hydroxide, sodium hydroxide orpotassium hydroxide, of a concentration of about 2 to 30 percent byweight, preferably 10 to percent by weight. It is preferred the contentof maleic acid in the copolymer range from about 40 to 60 percent on amolar basis, because, the viscosity of a coating solution is too highduring the application thereof for forming the surface layer if themaleic acid content is too high, while the compatibility of thecopolymer with gelatin deteriorates if the maleic acid content is toolow. A suitable amount of the copolymerizable monomer which can bepresent can range from about 0.5 to 30 mole percent, preferably 1 to 10mole per-,

cent. Although the molecular weight of the copolymers is not limited andcan vary widely, copolymers having a molecular weight of about 10 to 10and particularly 10 to 5 X 10" can be suitably used. Suitablepolymerization procedures which can be used are well known in the priorart, for example, as disclosed in W. R. Sorensen et al., PreparativeMethods of Polymer Chemistry, John Wiley and Sons, New York (1961).

Thus resulting copolymers are used as a component of the surface layer.In adding these copolymers to the surface layer, a preferred amountthereof ranges arom about 5 to percent by weight based on the totalweight of the binder in the top layer. Because, if the amount is lessthan about 5 percent, a sufficient effect can not be obtained and if theamount is above about 80 percent, the surface layer dissolves ondevelopment in alkaline developers. A suitable thickness for the toplayer generally ranges from about 0.1 to So, preferably 0.3 to 3,u..

, By addition of these copolymers to the surface layer, the occurrenceof reticulation can be inhibited. However, if these copolymers are usedtogether with matting agents, the anti-adhesive properties can beimproved. Accordingly, the surface layer can also contain matting agentssuch as polystyrene, polymethyl methacrylate, silica, starch powder,zinc carbonate, glass beads, cadmium carbonate, polyethyl acrylates,copoly-methyl methacrylate-butylacrylate, strontium carbonate, magnesiumoxide barium sulfate-strontium sulfate, titanium oxide, zirconium oxidea silver halide such as silver bromide, polystyrene, cellulosetriacetate, a calcium salt or magnesium salt of an acid such as analiphatic acid, an aromatic acid, an aromatic dicarboxylic acid such asterephthalic acid, a polycarbonate and the like. The most preferredmatting agents are silica, polymethyl methacrylate, a silver halide, andbarium sulfate-strontium sulfate. As the matting agents, those having aparticle size ranging from about 0.3 to 10a, particularly 0.5 to 3p. arepreferably used. In using these matting agents, they are used in theamount of about 0.1 to 10 percent by weight and preferably 0.5 to 3percent by weight based on the total weight of the binders in thesurface layer.

The binder of the surface layer can be selected, if desired, fromsynthetic and natural high molecular weight compounds such as gelatin,gelatin derivatives, polyvinyl alcohol, polyvinyl pyrrolidone,polyacrylamide, polyacrylic acid, polyacrylates, casein, agar agar,albumin, alginic acid, carboxycellulose alkyl esters, hydroxyethylcellulose, carboxyalkyl cellulose and the like. However, gelatin and thederivatives thereof are more preferable.

in applying these hydrophilic high molecular weight compounds with theabove described copolymers and the matting agents on the photographicmaterial, water,

organic solvents such as methanol, ethanol, propanol,

acetone, methyl ethyl ketone, etc., or mixtures thereof are used.However, water is advantageously used.

In addition, hardening agents as described in, e.g., C. E. K. Mees andT. H. James, The Theory ofthe Photographic Process, 3rd ed., pages 5560, Macmillan Co., 1966) and the hardening agents described in U.S. Pat.No. 3,316,095 are preferably used at application. Of these hardeningagents, those of an aldehyde type (including the mucochloric acid type,and the aldehyde precursor type), an active vinyl type, an activehalogen.

type, a carbodiimide type, an isoxazole type, an epoxy type, anaziridine type and an inorganic type provide better results.Particularly, the following hardening agents exhibit particularlyexcellent results. Aldehyde type:

Mucochloric acid, mucobromic acid, mucophenoxychloric acid, mucophenoxybromic acid, formaldehyde,

dimethylol urea, trimethylolmelamine, 1,3-bis-[(diallylamino)-methyll-urea, 1,3-bis- (piperidinomethyl)-urea, glyoxal,monomethylglyoxal, 2,3-dihydro-1,4-dioxane, 2,3-dihydroxy-5-methyl-l ,4-dioxane, succinaldehyde, 2,5-dimethoxytetrahydrofuran andglutaraldehyde.

Active vinyl type:

1,3,5-Triacryloyl-hexahydro-s-triazine and 1,3,5-trivinylsulfonyl-hexahydro-s-triazine. Active halogen type:

2,4-Dichloro-6-(4-sulfoanilino)-l,3,5-triazine so dium salt,2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt and2,4-dichloro-6-(2-sulfoethylamino)- 1,3,5-triazine sodium salt.

Carbodiimide type:

Dicyclohexylcarbodiimide, 1-cyclohexyl-3-( 3- trimethylaminopropyl)-carbodiimide-p-toluenesulfonate and l-ethyl-3-( 3-dimethylaminopropylcarbodiimide hydrochloride.

Isoxazole type:

2,5-Dimethylisoxazole perchlorate, 2-ethyl-5-phenylisoxazole-3'-sulfonate and 5 ,5 p-phenylene bisisoxazole.

Epoxy type:

1,4-bis-(2',3 -Epoxypropoxy)-butane tricresylisocyanurate.

Aziridine type:

l,6-Hexamethylene-N,N-bisethyleneurea and 2,4,6-triethyleneimino-l,3,5-triazine.

Inorganic type:

Chromium alum and chromium acetate.

These hardening agents can be added using conventional methods. Forexample, a hardening agent dissolved in water or an organic solvent isdirectly added to the composition used to form the surface layer, or ahardening agent is added in a large amount to an another layer so as todiffuse into the surface layer.

Although the amount of these hardening agents depends upon a desiredobjects, they can be used in the amount of about 2 to about 80 mg andpreferably 5 to mg per gram of gelatin.

Furthermore, as coating assistants, sodium dodecyl benzene sulfonate,sodium N-oleyl-N-methyltaurine, sodium l4-p-nonyl-phenyl-5,8,l1,14-tetraoxatetradecane sulfonate andN-tetradecyl-N,N-dimethylammonioacetate can be used.

The contents of the high molecular weight compounds, gelatin, thematting agents, lubricating agents, antistatic agents, the hardeningagents and the coating assistants in the present invention can be variedover a broad range depending on the requirements of quality and end-useof the photographic sensitive materials. The specific agents and theoptimum amounts thereof can be easily determined by persons skilled inthe art.

It is important to choose a method of application in order to increaseproductivity. For example, clip coating, air knife coating, curtaincoating and extrusion coating can be advantageously utilized. The toplayer of this invention is applicable to black and white, multi layercolor, X-ray and the like photographic materials utilizing any layerstructure. The top layer can be a surface layer on the photosensitivelayer side of the support or a surface layer on the opposite side of thesupport to the photosensitive layer.

and 1,3,5-

As development processing solutions, any developer can be used if it canreduce halide particles. In the case of black white development,developers containing polyhydroxybenzenes, N-alkylaminophenols,l-phenyl- 3-pyrazolidones or a mixture thereof can be used. Examples ofpolyhydroxybenzenes include hydroquinone, pyrocatechol, pyrogallol andthe like. Examples of N- monoalkylaminophenols include N-methylaminophenol, N-ethylaminophenol and the like. Examples ofl-phenyl-3-pyrazolidones include l-phenyl-3-pyrazolidone,l-phenyl-4,4-dimethyl-3- pyrazolidone and the like. In the case of colordevelopment, developers containing p-phenylenediamine derivatives suchas 4-amino-N,N-diethylaniline. 4-amino-3-methyl-N-methyl-N-(,B-methanesulfonamidoethyl- )aniline,4-amino-3-methy|-N-ethyl-N-(B-hydroxyethyl)-aniline and the like can beused as a developing agent.

In the following, examples of the synthesis of compounds are illustratedin detail. Unless otherwise indicated herein, all parts, percents,ratios and the like are by weight.

Synthesis of Compound 1 500cc of p-cymene, 49g (0.5 mols) of maleic acidanhydride, 52g (0.5 mols) of styrene and 0.5g of azobisisobutyronitrilewere charged into a 1-liter 3-neck flask equipped with a stirrer, anitrogen gas inlet and a reflux condenser. After sufficiently replacingdissolved oxygen by nitrogen gas, the mixture was heated to C for about6 hours with stirring. The resulting high molecular weight compound wasseparated by filtration and dried under a vacuum until a constant weightwas obtained. As the result of elementary analysis and alkali titration,the resulting high molecular weight compound had a styrene content of48.7 mol percent. The yield was 96.2g (95.3 percent). Then the highmolecular weight compound was hydrolyzed using an aqueous solution ofsodium hydroxide to produce a 20 percent solution. The pH was 6.3. Asthe result of a determination of the viscosity, the solution had aviscosity of; sp/c 0.61 (30C).

Synthesis of Compound 2 A polymerization reaction was carried out in thesame manner as for the above described Compound 1 but 50cc of acetone,50cc of methanol, 62.4g (0.6 mols) of styrene, 69.6g (0.6 mols) ofmaleic acid and 1.3g of benzoyl peroxide as a polymerization initiatorwere used. Namely,,the mixture was heated to 60 to 70C for 5 hours withstirring.

The reaction product was reprecipitated using water and dried in avacuum until a constant weight was obtained. The yield was g (91.0percent). AS the result of elementary analysis, the compound was foundto contain 57 mol percent styrene (C: 69.2 percent). Then the resultingcopolymer was neutralized to make a 20 percent aqueous solution. The pHwas 6.8 and the viscosity was 4 sp/c=0.49.

Synthesis of Compound 3 50cc of acetone, 5000 of methanol, 62.4g (0.6mols) of styrene, l 16g (1.0 mol) of maleic acid and 1.5 g of benzoylperoxide as the polymerization initiator were charged into a reactor.After replacing the dissolved oxygen by nitrogen gas, the mixture wasstirred at 60 to 70C for 3 hours. The product was reprecipitated usingwater and dried in a vacuum until a constant weight was obtained. Theyield was 95.2g (54.5 percent). As the result of elementary analysis, itwas found to contain 47.5 mol percent styrene. The dried product wasneutralized with a sodium hydroxide solution to amples.

EXAMPLE 1 On a triacetyl cellulose base film having a subbing layer, ared-sensitive emulsion layer, an intermediate layer, a green-sensitiveemulsion layer, a yellow filter IO layer, a blue-sensitive emulsionlayer and a top layer were formed by application, wherein these layerscontained the additives shown in Table 1. However, the top layer wasformed by preparing compositions l, 2, 3, 4

and 5 by mixing gelatin as a binder and Compound 1 so that the ratio ofCompound 1 was 0, 20, 40, 60 or 80 percent by weight, adding to theresulting composi- In this processing, the temperature was maintained ator 50C.

Color Development 3 Bleach 6 Water Wash 3 Fixing 6' Water Wash 3'Stabilizing Bath 3' The compositions of the color negative processingsolutions were as follows.

Color Developing Solution:

tions 25 mg of 2,4,6-triethyleneimino-l,3,5-triazine as Sodium Sulfate2.0 g

a hardening agent, and 20 mg of silicon dioxide partiggi i'g ggg g g"2-8 g cles and 20 mg of polymethyl methacrylate particles as 20 lAlcohol matting agents per lg of gelatin, applying the composi-Hydrqxylamiflc Sulfate g tions and drying (the thickness of the toplayer after 3:923

drying being 1 2g). Water to make I 1 TABLE 1 Layer Structure(additives, thickness) Red-Sensitive Emulsion Layer Green-SensitiveEmulsion Layer Blue-Sensitive Emulsion Layer Color Form-4-Chloro-N-nl-2,4,6-Trichloro- 3-(2,4-Di-amyling Agentdodecyl-l-hydroxyphenyl-3-(3-(aphenoxyacetamldo)- naphthamide (890)2,4-di-t-amyla-(4-methoxybenzoyl) phenoxy )acetamido) acetanilide l 300)benzamido-5 pyrazolone Spectral bis-(9-Ethyl-5- bis-(9-Ethyl-5- NoneSensitizer chloro-3-hydroxyphenyl-B-ethyl)ethyl)thiacarbooxycarbocya'nme cyanine bromide lsothlocyanate (7.0)(5.5) Stabilizer 5-Methyl-7-hydroxy- Same Same 2,3,4-triazaindolizine(8.0) (8.2) (7.0) Hardening 2,4.6-Triethylene- Same Same Agentimino-l,3,S-triazine (48) (65) Coating Sodium dodecylbenzene Same SameAssistant sulfonate (45 (50) (70) Sodium nonylphenoxy- Same Samepolyethylene oxypropane sulfonate Note: The figures in parentheses meanmg per square meter.

Intermediate Layer: so Bleaching Solution:

A gelatin solution was applied in a thickness of 2p. so SodiumlwgElhilcflcdiflminc Tetrflacewle -0 E I I Potassium romi c 60.0 g as toinclude 35 mg of the hardening agent shown m Ammonium Hydroxide (28%)500 ml Table l, 60 mg of sodium dodecylbenzene sulfonate Glacial AceticAcid 25.0 m and 75 mg of sodium nonylphenoxy-polyethyleneoxy- Water l lpropane per square meter. 55 Yellow Filter Layer: Fixing Solution:

A gelatin solution was applied in a thickness of 211. so Sodium Sulfate10.0 g as to include 35 mg of the hardening agent shown in a Thluiulfme20:10 E

. ll 01' 0 ma C Table 1, 65 mg of the above described coating assistantI and 82 mg of yellow colloidal silver per square meter. 60 SilverHalide Emulsion: lo 0 ml A silver iodobromide emulsion (iodine: 5.5percent s l by mol).

After these samples were stored at 25C and a humidity of 60 percent for1 week, they were subjected to 65 color negative processing. Then thedegree of reticulation was observed on each sample.

The degree of the occurrence of reticulation of the photographicmaterials after processing are shown in Table 2.

TABLE 2 Temperature of Treatment Temperature and Effect Sample No. l 2 34 2 5C A A A A A 30C C A A A A 3 5C C B A A B 40C C C B A D 50C C C C BD In the table. A. B. C and D each are as follows.

A Reticulation was not observed at all.

B Retieulation was observed slightly.

C Retieulation was observed considerably.

D The top layer dissolved.

EXAMPLE 2 Compound 2 was added to each sample of Example 1 as follows,and the samples were produced by application and drying.

Sample 1:

No layers contain Compound 2. Sample 2:

30 percent in the intermediate layer and the yellow filter layer wasreplaced by Compound 2.

Sample 3:

30 percent of gelatin in all of the layers except the top layer wasreplaced by Compound 2.

Sample 4:

30 percent of gelatin in only the top layer was substituted by Compound2.-

Sample 5:

30 percent of the layers was replaced by Compound 2.

After these samples were stored at C and humidity of 60 percent for 1week, the same processing as in Example 1 was carried out, and thenreticulation was observed. The degree of the occurrence of reticulationis shown in Table 3.

TABLE 3 Temperature and Effect Sample No. l 2 3 4 5 Temperature ofTreatment 25C A A A A A C B B A A A 3 5C C C C A A 40C C C C A A 45C C CC B B (A. B and C have the same meanings as defined in Example I.)

EXAMPLE 3 On a polyethylene terephthalate base film having a subbinglayer, a red-sensitive emulsion layer, a greensensitive emulsion layer,a yellow filter layer, a bluesensitive emulsion layer and a top layerwere formed by application using the spectral sensitizers, thestabilizer and the coating assistants shown in Table 1 and 20 mg ofmucochloric acid per gram of the binder as a hardening agent. The toplayer was formed by preparing samples 1, 2, 3 and 4 by mixing silverhalide particles and barium sulfate as matting agents, liwuid paraffinas a lubricating agent and Compound 3 in an amount of O, 5, 30 orpercent by weight based on the binder weight in addition to theabove-described coating assistants and the hardening agent, applying themixture and drying (the thickness of the top layer being 1 2,u.).

After these samples were stored at 25C and a humidity of percent for 1week, the following reversal color processing was carried out by varyingthe period of time for color processing over a range of 10 to 50seconds. After processing, the degree of reticulation was examined.

The compositions of each processing bath were produced using knownmethods (as disclosed in US. Pat. No. 3,723,125).

in greater detail, the composition of the prehardening bath was asfollows.

Sodium Hexametaphosphate 2 g Sodium Bisulfltc 5 g Sodium Pyrophosphate(deea hydrate) 15 g Glauber Salt (anhydrous) g Potassium Bromide 2 gSodium Hydroxide 0.1 g Formalin (37%) 17 ml Water to make 1000 ml Thedegree of reticulation occurrence is shown in Table 4.

TABLE 4 Time of Time of Processing and Effect Pre-hardening Sample No.

(Seconds) 1 2 3 4 l() C C C B 20 C C B A 30 C C A A 40 C A A A 50 B A AA It can be understood from the results in Table 4 that reticulationoccurs with difficulty if a part of the binder in the top layer isreplaced by Compound 3, even though the time for the pre-hardeningtreatment is remarkably short,

EXAMPLE 4 In this example, samples corresponding to Sample 1 and Sample2 of Example 2 were prepared except that silicon dioxide and polymethylmethacrylate particles were not used. Sample 6 and Sample 7 wereprepared in the same manner as in Sample 1 and Sample 3 of Example 2.

The resulting Sample 6 and Sample 7 and Sample 1 ,and Sample 2 ofExample 2 were tested with respect to the degree of adhesion. Theadhesion test was carried out as follows. Each sample was cut to maketwo sheets of 2cm X 2cm. These sheets were individually placed at aspecific temperature and a specific humidity and were placed so as tonot contact each other. After being maintained at such conditions for 2days, the two sheets of the sample were superposed so that top layer ofone faced the back layer of the other. After a weight of 200g was put onthe superposed sheets (5Og/cm the sheets were kept at the sameconditions for 1 day. Then the sheets were peeled off and the area ofadhesion was measured. In Table 5, the percentages of the area ofadhesion based on the total area are shown.

Condition: Relative Humidity 90% From the results shown in Table 5, itcn be understood by comparison of Samples 1 and 3, of Samples 6 and 7,of Samples 1 and 6 and of Samples 3 and 7 that l the anti-adhesiveproperty is improved if a part of gelatin in the top layer is replacedby Compound 1 and (2) the anti-adhesive property is remarkably improvedif matting agents are additionally added thereto.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:

1. A method of forming photographic images which comprises developing atabove 30C a photographic one material comprising a support havingthereon at least on photosensitive emulsion layer and a surface layercomprising a hydrophilic binder and containing a copolymer includingrepeating units represented by the formula (l) CH2 ca and repeatingunits represented by the formula (H) wherein R represents a hydrogenatom or a methyl group, and M and M each represents a member selectedfrom the groupconsisting of a hydrogen atom, a lithium atom, a sodiumatom, a potassium atom and an ammonium group, whereby occurrence ofreticulation decreases and anti-adhesive properties are improved.

2. The method of forming images of claim 1, wherein said copolymercontains about 40 to 60 percent on a molar basis of the repeating unitsrepresented by the formula (I) and about 60 to 40 percent on a molarbasis of the repeating units represented by the formula (ll).

3. The method of forming images of claim 1, wherein said surface layercomprises a protective layer which substantially does not formphotographic images.

4. The method of forming images of claim 1, wherein the proportion ofsaid copolymer to said hydrophilic binder in said surface layer rangesfrom about 5:95 to about :20.

5. The method of forming images of claim 4, wherein said hydrophilicbinder comprises a natural or synthetic high molecular weight material.

6. The method of fonning images of claim 5, wherein said binder isgelatin, albumin, agar agar, a gelatin derivative, a cellulosederivative, polyvinyl alcohol, a partial ester of polyvinyl alcohol,polyacrylamide, polyvinyl pyrrolidone, polyacrylic acid or apolyacrylate.

7. The method of forming images of claim 1, wherein the surface layercontains a hardening agent for said hydrophilic binder.

ing compound, an active vinyl compound or an inorganic hardening agent.

9. The method of forming images of claim 1, wherein the surface layerincludes a matting agent.

10. The method of forming images of claim 9, wherein the amount of thematting agent ranges from about 0.1 to 10 percent by weight based on thetotal binder weight of the surface layer. a l

1. A METHOD OF FORMING PHOTOGRAPHIC IMAGES WHICH COMPRISES DEVELOPING ATABOVE 30*C A PHOTOGRAPHIC ONE MATERIAL COMPRISING A SUPPORT HAVINGTHEREON AT LEAST ONE PHOTOSENSITIVE EMULSION LAYER AND A SURFACE LAYERCOMPRISING A HYDROPHILIC BINDER AND CONTAINING A COPOLYMER INCLUDINGREPEATING UNITS REPRESENTED BY THE FORMULA (I)
 2. The method of formingimages of claim 1, wherein said copolymer contains about 40 to 60percent on a molar basis of the repeating units represented by theformula (I) and about 60 to 40 percent on a molar basis of the repeatingunits represented by the formula (II).
 3. The method of forming imagesof claim 1, wherein said surface layer comprises a protective layerwhich substantially does not form photographic images.
 4. The method offorming images of claim 1, wherein the proportion of said copolymer tosaid hydrophilic binder in said surface layer ranges from about 5:95 toabout 80:20.
 5. The method of forming images of claim 4, wherein saidhydrophilic binder comprises a natural or synthetic high molecularweight material.
 6. The method of forming images of claim 5, wheReinsaid binder is gelatin, albumin, agar agar, a gelatin derivative, acellulose derivative, polyvinyl alcohol, a partial ester of polyvinylalcohol, polyacrylamide, polyvinyl pyrrolidone, polyacrylic acid or apolyacrylate.
 7. The method of forming images of claim 1, wherein thesurface layer contains a hardening agent for said hydrophilic binder. 8.The method of forming images of claim 6, wherein said binder is gelatinand said hardening agent is an aldehyde hardening agent, a methylolgroup or alkylaminomethyl group containing formaldehyde precursor, a1,4-dioxane hardening agent, an aziridine hardening agent, an isoxazolehardening agent, a carbodiimide hardening agent, an active halogencontaining compound, an active vinyl compound or an inorganic hardeningagent.
 9. The method of forming images of claim 1, wherein the surfacelayer includes a matting agent.
 10. The method of forming images ofclaim 9, wherein the amount of the matting agent ranges from about 0.1to 10 percent by weight based on the total binder weight of the surfacelayer.